Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
  • G03C2001/0471—Isoelectric point of gelatine
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/151—Matting or other surface reflectivity altering material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/162—Protective or antiabrasion layer

Definitions

• This invention relates to a silver halide photographic light-sensitive material and more particularly, to a silver halide photographic light-sensitive material which has improved processing properties and surface characteristics.
• photographic light-sensitive materials natural hydrophilic high molecular weight materials such as gelatin and/or synthetic hydrophilic high molecular weight materials are usually contained in a silver halide emulsion layer, photographic auxiliary layers such as an intermediate layer, a protective layer and an antihalation layer, and a subbing layer interposed between the above layers and a support.
• Photographic light-sensitive materials containing hydrophilic high molecular weight materials are usually processed, to form photographic images after exposure with various aqueous solutions having different pH's and salt concentrations at different temperatures for development, stopping, fixing, washing and the like (bleaching is also conducted for color light-sensitive materials).
• the photographic light-sensitive material is processed at a higher temperature as in rapid processing, i.e., the procedures used to form images through rapid development and other photographic processings, or when processing requires a long time since the processing includes many steps for various purposes as in the processing of color reversal photographic materials, many disadvantages occur.
• the photographic light-sensitive emulsion layers and other layers swell excessively and soften, thus with the physical strength being reduced and often resulting in the occurrence of a reticulate pattern, which is referred to as reticulation, on the surface thereof.
• incorporation of a large amount of a hardening agent, such as several times to about twenty times the conventional amount, in a photographic light-sensitive emulsion layer or a protective layer in preparing a photographic light-sensitive material, thus imparting, to the photographic light-sensitive material, physical strength to withstand severe processing conditions has previously been considered.
• this method prevents the occurrence of reticulation to some extent, a substantially complete prevention is not achieved and, in addition, a phenomenon known as "after-hardening", in which the physical strength of an emulsion film gradually changes during the storage of the photographic light-sensitive material, tends to occur, so that maintenance of photographic qualities is difficult.
• this method has the disadvantage that the penetration and diffusion of a developer are hindered in development processing because the degree of hardening of the photographic layers is too high and, thus, sensitivity is substantially reduced.
• a photographic light-sensitive material after exposure to processing with a bath of an aqueous solution containing a hardening agent, which is referred to as a prehardening bath, immediately before development, or to carry out development and hardening at the same time using a developer also containing a hardening agent.
• these methods have the defects that undesirable results such as fog, a deterioration of other photographic properties, or color contamination, particularly, in color light-sensitive materials, are obtained in using certain types of hardening agents, and that in order to provide photographic layers having the required physical strength within a short processing time without deteriorating the photographic properties, the kind of a hardening agent, as well as the kind of a light-sensitive material applicable, and processing conditions are narrowly restricted.
• the method involving processing with a prehardening bath is not a very good technique to use in shortening the photographic processing time and simplifying the processing steps because the number of processing steps is increased.
• carboxymethylated casein or ethyl cellulose sulfate sodium salt in place of a gelatin protective layer, is previously coated as an uppermost layer on the emulsion layer side of a photographic light-sensitive material (e.g., as described in U.S. Defensive Publication T887,012).
• This method is considered to be advantageous in that it is not necessary to incorporate a large amount of a hardening agent in a photographic layer.
• carboxymethylated casein is disadvantageous in that removal therefrom of impurities which have an undesirable effect on photographic properties is difficult, and also, from the viewpoint of the preparation of a photographic light-sensitive material, that it is difficult to form a uniform coated layer on an emulsion layer using an aqueous solution of carboxymethylated casein.
• ethyl cellulose sulfate sodium salt having good solubility in water is difficult to produce with satisfactory reproducibility.
• ethyl cellulose sulfate sodium salt also has the defects, for example, that the material has poor long-term storage stability, as might be supposed from the chemical structure of sulfate esters, and also the material is not settable, which is the ability to solidify on cooling after coating, and has poor coating properties. Therefore, ethyl cellulose sulfate sodium salt is not always suitable as a component for use in the preparation of a photographic light-sensitive material.
• Silver halide photographic materials usually have a surface layer containing a hydrophilic colloid, of which gelatin is representative, as a binder. Therefore, under high temperature and high humidity conditions the surface of the photographic materials has increased adhesiveness or tackiness and, thus, the photographic materials easily adhere to other materials on contact therewith. This adhesion happens between photographic materials or between the photographic material and another object which contacts the photographic material during the preparation of the photographic materials, photographing, processing, projection and storage, which often causes various problems.
• a method which overcomes the above-described problem and is well known to those skilled in the art involves incorporation of an inorganic material such as silicon dioxide, magnesium oxide, titanium dioxide or calcium carbonate, or finely divided particles of an organic material such as polymethyl methacrylate or cellulose acetate propionate in a surface layer, thereby coarsening the surface layer, that is, forming a so-called matted surface, and thus decreasing the adhesiveness.
• an inorganic material such as silicon dioxide, magnesium oxide, titanium dioxide or calcium carbonate
• finely divided particles of an organic material such as polymethyl methacrylate or cellulose acetate propionate
• An object of this invention is to provide a photographic light-sensitive material which can be used to rapidly form images of a high quality by photographic processings.
• Another object of this invention is to provide a photographic light-sensitive material having excellent adhesion resistance in which reticulation by processing at higher temperatures does not occur.
• a further object of this invention is to provide a photographic light-sensitive material having excellent adhesion resistance in which adhesion difficulties during the preparation of the light-sensitive material seldom or never occur.
• the photographic light-sensitive material of this invention comprises a support having at least one photographic layer thereon, and at least one of the photographic layers contains acid-processed gelatin and a matting agent.
• the photographic layers used herein include a silver halide photographic emulsion layer, a protective layer, a backing layer, an intermediate layer, an antihalation layer, and the like.
• a particularly preferred embodiment of this invention is a photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer and an uppermost layer coated thereon, the uppermost layer containing acid-processed gelatin and a matting agent.
• uppermost layer means a layer which is a surface layer of those layers constituting the photographic light-sensitive material.
• a layer such as an intermediate layer or an antihalation layer which does not ultimately form a surface layer can be, in a sense, called an uppermost layer. That is, in preparing the photographic light-sensitive material of this invention, each of the layers may be successively coated on one or more layers, and a layer at the surface in each step can be considered to be an uppermost layer.
• the uppermost layer can be provided on both sides of a support.
• the thickness of the uppermost layer preferably ranges from about 0.2 to 5 ⁇ , particularly 0.5 to 3 ⁇ .
• the acid-processed gelatin used in this invention is gelatin produced from collagen using a production process including a processing with hydrochloric acid, etc., and differs from alkali-processed gelatin which is generally used in the photographic industry and is produced using a production process including a processing with lime, etc. Details of the processes for producing these gelatins and the properties thereof are described in Arthus Veis, The Macromolecular Chemistry of Gelatin, pages 187-217, Academic Press (1964), and the most important difference is that acid-processed gelatin has an isoelectric point of a pH of about 6.0 to 9.5 while alkali-processed gelatin has an isoelectric point of a pH of about 4.5 to 5.3.
• the uppermost layer contains acid-processed gelatin, but the layers other than the uppermost layer need not necessarily contain acid-processed gelatin.
• a layer containing acid-processed gelatin can be coated as an uppermost layer of a photographic light-sensitive material having a usual protective layer.
• hydrophilic binders which can be used include alkali-processed gelatin, as well as enzyme-processed gelatin produced using a processing with an enzyme in the process of producing gelatin, a so-called gelatin derivative, that is, a product prepared by treating and modifying the functional groups contained in the gelatin molecule, such as amino groups, imino groups, hydroxyl groups or carboxyl groups, with a compound having a group capable of reacting with such a functional group, and a graft polymer prepared by grafting the molecular chain of another high molecular weight material to gelatin.
• a so-called gelatin derivative that is, a product prepared by treating and modifying the functional groups contained in the gelatin molecule, such as amino groups, imino groups, hydroxyl groups or carboxyl groups, with a compound having a group capable of reacting with such a functional group, and a graft polymer prepared by grafting the molecular chain of another high molecular weight material to gelatin.
• Compounds which can be used for producing the above-described gelatin derivatives include, e.g., the isocyanates, acid chlorides and acid anhydrides as described in U.S. Pat. No. 2,614,928; the acid anhydrides as described in U.S. Pat. No. 3,118,766; the bromoacetic acids as described in Japanese Patent Publication No. 5,514/64; the phenylglycidyl ethers as described in Japanese Patent Publication No. 21,845/67; the vinylsulfone compounds as described in U.S. Pat. No. 3,132,945; the N-allylvinylsulfonamides as described in British Pat. No.
• chain polymers which can be used for grafting to gelatin are disclosed, for example, in U.S. Pat. Nos. 2,763,625, 2,831,767 and 2,956,884, Polymer Letters, 5, 595 (1967), Photographic Science and Engineering, 9, 148 (1965), Journal of Polymer Science, A-1, 9, 3199 (1971), etc.
• polymers and copolymers of the so-called vinylic monomers such as acrylic acid, methacrylic acid, derivatives of acrylic acid and derivatives of methacrylic acid such as the esters, amides and nitriles thereof, and styrene can be used for this purpose.
• Hydrophilic vinylic polymers which are somewhat compatible with gelatin, for example, polymers or copolymers of acrylic acid, acrylamide, methacrylamide, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, etc., are particularly preferred.
• suitable hydrophilic binders include proteins such as colloidal albumin or casein, cellulose derivatives such as carboxymethyl cellulose or hydroxyethyl cellulose, polysaccharides such as agar-agar, sodium alginate, dextran, gum arabic or starch derivatives, and synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polymethacrylic acid copolymer, polyacrylamide or polymethacrylamide, derivatives thereof and the partially hydrolyzed products thereof. If desired, a compatible mixture of two or more of these colloids can be used.
• gelatin derivatives and synthetic high molecular weight materials having carboxyl group or salt thereof are particularly preferred because they have a high controlling effect on the occurrence of reticulation.
• the acid-processed gelatin is used in an amount of more than about 20 wt%, particularly more than 40 wt%, based on the total weight of the binders forming the uppermost layer.
• the content of the acid-processed gelatin is less than about 20 wt%, and alkali-processed gelatin, enzyme-processed gelatin or a gelatin derivative is not present as the other binders, the coating solution is difficult to set (solidify) by cooling after coating, and it is, thus, difficult to obtain a uniformly and smoothly coated surface.
• the objects of this invention are satisfactorily accomplished by further incorporating a matting agent in an uppermost layer containing, at least, acid-processed gelatin.
• Matting agents are powders of an organic or inorganic material, and the average particle size thereof is preferably about 0.2 to 10 ⁇ , particularly 0.3 to 5 ⁇ .
• Preferred specific examples of matting agents include organic materials such as water-dispersible vinyl polymers such as polymethyl methacrylate, cellulose acetate propionate and starch, etc., and inorganic materials such as silver halide, strontium barium sulfate, calcium carbonate, silicon dioxide, magnesium oxide and titanium oxide, etc.
• the matting agents described above are incorporated in an uppermost layer containing acid-processed gelatin in an amount of about 1 to 100 mg, preferably 5 to 30 mg, per g of the binder(s).
• the use of the matting agent incorporated in the uppermost layer containing acid-processed gelatin provides an adhesion resistance which is remarkably superior to that obtained with the use of the matting agent in combination with alkali-processed gelatin only. This enables a substantial reduction in an amount of the matting agent which needs to be incorporated, so that after processing such photographic light-sensitive materials, images having excellent transparency and graininess can be obtained.
• an appropriate amount of a hardening agent or a lubricant can be used together with the binders forming an uppermost layer. It is well known to incorporate these additives for gelatin into an uppermost layer of a conventional photographic light-sensitive material as the means necessary for using the uppermost layer more effectively, and these additives can also be used in this invention for the same purposes.
• a suitable amount of the hardening agent which can be employed ranges from about 2 to 80 mg, preferably from about 5 to 20 mg, per g of the binders employed in the uppermost layer, and a suitable amount of the lubricant ranges from about 1 to 100 mg, preferably from about 10 to 50 mg, per g of the binders employed in the uppermost layer.
• the hardening agents are effective for maintaining the physical strength of a surface layer by moderately hardening an uppermost layer
• suitable hardening agents are aldehyde compounds such as formaldehyde or glutaraldehyde; ketone compounds such as diacetyl or cyclopentanedione; compounds containing reactive halogens such as bis(2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine, compounds as described in U.S. Pat. Nos. 3,288,775 and 2,732,303, and British Pat. Nos.
• reactive olefin compounds such as divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine or compounds as described in U.S. Pat. Nos. 3,635,718 and 3,232,763, and British Pat. No. 994,869
• N-methylol compounds such as N-hydroxymethylphthalimide or compounds as described in U.S. Pat. Nos. 2,732,316 and 2,586,168
• isocyanates as described in U.S. Pat. No. 3,103,437
• aziridine compounds as described in U.S. Pat. Nos. 3,017,280 and 2,983,611
• acid derivatives as described in U.S.
• hardening agent precursors such as alkali metal bisulfite-aldehyde adducts, methylol derivatives of hydantoin or primary aliphatic nitroalcohols can be used.
• Lubricants are useful for preventing adhesion due to an effect similar to that exhibited by the matting agents, and also are effective for improving the friction characteristics, particularly in the compatibility with a camera on photographing or on projection of movie films.
• Specific examples of preferred lubricants which can be used include waxes such as liquid paraffin and esters of higher aliphatic acids, polyfluorinated hydrocarbons and derivatives thereof, and silicones such as polyalkyl polysiloxanes, polyaryl polysiloxanes and polyalkylaryl polysiloxanes, and the alkylene oxide addition derivatives thereof.
• Surface active agents can also be added, individually or as a mixture thereof, e.g., in an amount of from about 0.5 to 50 mg, preferably 1 to 20 mg, per g of the binders employed, to a dispersion used for forming an uppermost layer. They are generally used as a coating aid for preventing the occurrence of difficulties such as unevenness in coating, but they are sometimes employed for other purposes, for example, for improving emulsification and dispersion, for preventing the formation of static charges and adhesion to a finished light-sensitive material, or the like.
• These surface active agents can be classified as natural surface active agents such as saponin; nonionic surface active agents such as alkylene oxide, glycerol or glycidol nonionic surface active agents; cationic surface active agents such as higher alkylamines, quaternary ammonium salts, pyridinium or other heterocyclic onium salts, phosphoniums or sulfoniums; anionic surface active agents containing acid groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric ester or phosphoric ester groups; and amphoteric surface active agents such as amino acids, aminosulfonic acids, or sulfuric or phosphoric esters of aminoalcohols.
• nonionic surface active agents such as alkylene oxide, glycerol or glycidol nonionic surface active agents
• cationic surface active agents such as higher alkylamines, quaternary ammonium salts, pyridinium or other heterocyclic onium salts
• the photographic light-sensitive materials of this invention can contain the following components and can be prepared by the production methods described below.
• Silver halide emulsions are usually prepared by mixing a solution of a water-soluble silver salt (such as silver nitrate) with a solution of a water-soluble halide (such as potassium bromide) in the presence of a solution of a water-soluble high molecular weight material such as gelatin.
• a water-soluble silver salt such as silver nitrate
• a water-soluble halide such as potassium bromide
• Silver halides which can be used include silver chloride, silver bromide, as well as mixed silver halides such as silver chlorobromide, silver bromoiodide or silver chlorobromoiodide.
• the silver halide grains can be prepared using conventional methods. Of course, the grains can be advantageously prepared using the so-called single or double jet method, controlled double jet method, and the like. Moreover, two or more of silver halide photographic emulsions, separately prepared, can be mixed, if desired.
• the crystal structure of the silver halide grains can be uniform throughout the grain, can have a stratified structure in which the interior and outer portion are different, or can be of the so-called conversion type as described in British Pat. No. 635,841 and U.S. Pat. No. 622,318.
• the silver halides can be of the type in which a latent image is formed mainly on the surface of the grains or of the type in which a latent image is formed in the interior of the grains thereof.
• the silver halide grains are, after the formation thereof, washed with water to remove the water-soluble salts produced as by-products (for example, potassium nitrate when silver bromide is prepared using silver nitrate and potassium bromide) from the system and then heat treated in the presence of a chemical sensitizer such as sodium thiosulfate, N,N,N'-trimethylthiourea, gold(I) thiocyanate complex, gold(I) thiosulfate complex, stannous chloride or hexamethylenetetramine to increase the sensitivity without coarsening the grains.
• a chemical sensitizer such as sodium thiosulfate, N,N,N'-trimethylthiourea, gold(I) thiocyanate complex, gold(I) thiosulfate complex, stannous chloride or hexamethylenetetramine to increase the sensitivity without coarsening the grains.
• Conventional sensitizing methods are described in Mees and James,
• Hydrophilic colloids which can be used as a vehicle for silver halide include gelatin, colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose or hydroxyethyl cellulose, polysaccharides such as agar-agar, sodium alginate or starch derivatives, and synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers or polyacrylamide, and the derivatives thereof and the partially hydrolyzed products thereof. If desired, a compatible mixture of two or more of these hydrophilic colloids can be used.
• gelatin is most generally used, but gelatin can be, partially or completely, replaced with a synthetic high molecular weight material.
• the gelatin can be replaced with a so-called gelatin derivative, i.e., a product prepared by treating or modifying the functional groups contained in the gelatin molecule such as amino groups, imino groups, hydroxy groups or carboxyl groups with a compound having a group capable of reacting with such a functional group, or a graft polymer prepared by grafting the molecular chain of another high molecular weight material to gelatin.
• Compounds for producing the above gelatin derivatives include, e.g., isocyanates, acid chlorides and acid anhydrides as described in U.S. Pat. No. 2,614,928; acid anhydrides as described in U.S. Pat. No. 3,118,766; bromoacetic acids as described in Japanese Patent Publication No. 5,514/64; phenylglycidyl ethers as described in Japanese Patent Publication No. 26,845/67; vinylsulfone compounds as described in U.S. Pat. No. 3,132,945; N-allylvinylsulfonamides as described in British Pat. No. 861,414; maleinimide compounds as described in U.S. Pat. No.
• Chain polymers which can be used for grafting to gelatin are disclosed, for example, in U.S. Pat. Nos. 2,763,625, 2,831,767 and 2,956,884, Polymer Letters, 5, 595 (1967), Photographic Science and Engineering, 9, 148 (1965), Journal of the Polymer Science, A-1, 9, 3199 (1971), etc.
• polymers and copolymers of the so-called vinylic monomers such as acrylic acid, methacrylic acid, derivatives of acrylic acid and methacrylic acid such as the esters, amides and nitriles thereof, and styrene can be used for this purpose.
• Hydrophilic vinyl polymers which are somewhat compatible with gelatin, for example, polymers or copolymers of acrylic acid, acrylamide, methacrylamide, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, etc., are particularly preferred.
• synthetic polymer compounds such as a latex of water-dispersible vinyl compound polymers, particularly, compounds increasing the dimensional stability of the photographic material can be incorporated as such or as a mixture (e.g., of different polymers), or in combination with hydrophilic colloids which are permeable to water.
• synthetic polymer compounds are known, and are described, e.g., in U.S. Pat. Nos. 2,375,005, 2,739,137, 2,853,457, 3,062,674, 3,411,911, 3,488,708, 3,525,620, 3,635,715, 3,607,290 and 3,645,740, British Pat. Nos. 1,186,699 and 1,307,373, etc.
• the so-called graft-type emulsion-polymerized latices of these vinyl compounds which are prepared by subjecting such a vinyl compound to emulsion polymerization in the presence of a hydrophilic protective colloid high molecular weight material can be used.
• Suitable chemical sensitizers include, e.g., gold compounds such as chloroaurate or auric trichloride as described in U.S. Pat. Nos. 2,399,083, 2,540,085, 2,597,856 and 2,597,915; salts of noble metals such as platinum, palladium, iridium, rhodium or ruthenium as described in U.S. Pat. Nos. 2,448,060, 2,540,086, 2,566,245, 2,566,263 and 2,598,079; sulfur compounds capable of forming silver sulfide by reacting with a silver salt as described in U.S. Pat.
• gold compounds such as chloroaurate or auric trichloride as described in U.S. Pat. Nos. 2,399,083, 2,540,085, 2,597,856 and 2,597,915
• salts of noble metals such as platinum, palladium, iridium, rhodium or ruthenium as described in
• Various compounds can be added to the above photographic emulsions in order to prevent a reduction in sensitivity and the occurrence of fog during production of the light-sensitive material, during storage, and during processing.
• Many such compounds are well known, for example, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole, as well as a large number of heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, and the like. Examples of such compounds which can be used are described in C.E.K. Mees & T.H. James, supra and the original references cited therein, and also in the following patents: U.S. Pat. Nos.
• the photographic emulsion can be, if desired, spectrally sensitized or supersensitized using cyanine dyes such as cyanine, merocyanine or carbocyanine individually or in admixture, or in combination with, e.g., styryl dyes.
• cyanine dyes such as cyanine, merocyanine or carbocyanine individually or in admixture, or in combination with, e.g., styryl dyes.
• Such color sensitization techniques are well known and are described, e.g., in U.S. Pat. Nos. 2,493,748, 2,519,001, 2,977,229, 3,480,434, 3,672,897, 3,703,377, 2,688,545, 2,912,329, 3,397,060, 3,615,635 and 3,628,964, British Pat. Nos.
• the techniques can be optionally selected depending upon the purpose and end-use of the light-sensitive material, that is, the wavelength region to be sensitized, the sensitivity desired, and the like.
• a so-called diffusion-resistant coupler is present in the silver halide emulsion layer.
• suitable couplers are 4-equivalent or 2-equivalent diketomethylene yellow forming couplers such as the compounds as described in U.S. Pat. Nos. 3,415,625, 3,447,928, 3,311,476 and 3,408,194, the compounds as described in U.S. Pat. Nos. 2,875,057, 3,265,506, 3,409,439, 3,551,155 and 3,551,156, and the compounds as described in Japanese Patent Application (OPI) Nos.
• the silver halide emulsion can contain a dye-developing agent or a dye which can be bleached, and also can contain an ultraviolet absorbent, a fluorescent brightener, a dye for antihalation or filtering, etc.
• the photographic layers of this invention can be hardened using conventional procedures.
• suitable hardening agents include aldehyde compounds such as formaldehyde or glutaraldehyde; ketone compounds such as diacetyl or cyclopentanedione; compounds having reactive halogens such as bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine or those as described in U.S. Pat. Nos. 3,288,775 and 2,732,303, and British Pat. Nos.
• reactive olefin compounds such as divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, or those as described in U.S. Pat. Nos. 3,635,718 and 3,232,763, and British Pat. No. 994,869; N-methylol compounds such as N-hydroxymethylphthalimide, or those as described in U.S. Pat. Nos. 2,732,316 and 2,586,168; isocyanates as described in U.S. Pat. No. 3,103,437; aziridine compounds as described in U.S. Pat. Nos.
• hardening agent precursors such as alkali metal bisulfite-aldehyde adducts, methylol derivatives of hydantoin or primary aliphatic nitroalcohols can be used.
• the photographic layer of this invention can contain surface active agents, individually or in admixture. They are generally used as a coating aid, but they are sometimes employed for other purposes, for example, for improving emulsification and dispersion, sensitization or photographic characteristics, for prevention of the generation of static charges or adhesion, etc.
• surface active agents can be classified into natural surface active agents such as saponin; nonionic surface active agents such as alkylene oxide, glycerol or glycidol nonionic surfactants; cationic surface active agents such as higher alkylamines, quaternary ammonium salts, pyridines or other heterocyclic onium salts, phosphoniums or sulfoniums; anionic surface active agents containing acid groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric ester or phosphoric ester groups; and amphoteric surface active agents such as amino acids, aminosulfonic acids, or sulfuric or phosphoric esters of aminoalcohols.
• nonionic surface active agents such as alkylene oxide, glycerol or glycidol nonionic surfactants
• cationic surface active agents such as higher alkylamines, quaternary ammonium salts, pyridines or other heterocyclic onium salts, phospho
• the photographic emulsion layers and/or a backing layer can be coated, in this invention, on a support of such a substantially planar material which undergoes no marked changes in size during the course of processing.
• the layers are coated, for example, on a rigid support such as glass, metal or ceramics or a flexible support depending upon the end-use purpose.
• Typical examples of flexible supports are those which are generally used for photographic light-sensitive materials, such as cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, laminates of these films, thin glass films, and papers.
• supports such as papers coated or laminated with baryta or a polymer of an ⁇ -olefin, particularly having 2 to 10 carbon atoms, for example, polyethylene, polypropylene, ethylene-butene copolymers, etc., or synthetic resin films as described in Japanese Patent Publication No. 19,068/72 the surface of which has been roughened to improve the adhesion to other high molecular weight materials and improve printability.
• the supports can be transparent or opaque depending upon the end-use purpose of the light-sensitive material.
• the transparent supports can be colorless or can be colored with a dye or a pigment. Colored transparent supports have hitherto been employed in X-ray films and are described, e.g., in J. SMPTE, 67, 296 (1958).
• Suitable opaque supports include those which are intrinsically opaque, for example, papers, as well as films prepared by adding a dye or a pigment such as titanium oxide to a transparent film, synthetic resin films the surface of which has been treated in the manner as described in Japanese Patent Publication No. 19,068/72, and papers or synthetic resin films which are rendered completely light-shielding by the addition of carbon black, a dye, etc. If the adhesion between the support and the photographic emulsion layer is insufficient, a layer having good adhesion to both of these elements can be employed as a subbing layer.
• the surface of the support can be subjected to a pre-treatment such as a corona discharge, an ultraviolet irradiation, a flame treatment, and the like.
• the photographic layers of the photographic light-sensitive material can be coated using various coating methods including dip coating, air-knife coating, curtain coating, and extrusion coating using a hopper as described in U.S. Pat. No. 2,681,294. If desired, two or more layers can be coated at the same time using the techniques as described in U.S. Pat. Nos. 2,761,791, 3,508,947, 2,941,898 and 3,526,528.
• the photographic light-sensitive material of this invention has, essentially, a photographic layer containing acid-processed gelatin and a matting agent, and the remaining structure can be arranged in a conventional manner.
• the material can have a single emulsion layer or a number of emulsion layers, and can contain an intermediate layer, a filter layer, a subbing layer, an antihalation layer, etc. Therefore, the photographic light-sensitive material of this invention includes all types of photographic light-sensitive materials such as light-sensitive materials for black-and-white photography (for example, black-and-white photographic films, photographic papers, infrared films, X-ray films, lithographic films, dry plates, etc. and light-sensitive materials for color photography (for example, color positive films, color papers, color negative films, color reversal films, etc.).
• black-and-white photography for example, black-and-white photographic films, photographic papers, infrared films, X-ray films, lithographic films, dry plates, etc.
• the black-and-white light-sensitive material of this invention can be developed using conventional techniques.
• Developing agents which can be used include: 4-aminophenols such as 4-N-methyl-aminophenol hemisulfate (metol), 4-N-benzyl-aminophenol hydrochloride, 4-N,N-diethyl-aminophenol hydrochloride, 4-aminophenol sulfate, etc.; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 4-dimethyl-1-phenyl-3-pyrazolidone or 4-methyl-1-phenyl-3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, 2-methylhydroquinone, 2-phenylhydroquinone, 2-chlorohydroquinone, pyrogallol or catechol; p-phenylenediamines such as p-phenylenediamine hydrochloride or N,N-diethyl-p-phenylenediamine sul
• Typical examples of such other compounds include alkali agents such as the hydroxides, carbonates or phosphates of alkali metals or ammonia; pH modifiers or buffers, for example, weak acids such as acetic acid or boric acid, weak bases, or the salts thereof; development accelerators, for example, various pyridinium compounds, cationic compounds, potassium nitrate and sodium nitrate as described in U.S. Pat. Nos. 2,648,604 and 3,671,247, polyethylene glycol condensates and derivatives thereof as described in U.S. Pat. Nos. 2,533,990, 2,577,127 and 2,950,970, nonionic compounds such as polythioethers of which the compounds as described in British Pat. Nos.
• 1,020,033 and 1,020,032 are representative, organic amines such as pyridine or ethanolamine, benzyl alcohol, hydrazines, etc.; antifogging agents, for example, alkali metal bromides, alkali metal iodides, nitrobenzimidazoles as described in U.S. Pat. Nos. 2,496,940 and 2,656,271, as well as mercaptobenzimidazole, 5-methylbenztriazole, 1-phenyl-5-mercaptotetrazole, compounds for rapid processing as described in U.S. Pat. Nos.
• antioxidants such as sulfites, bisulfites, hydroxylamine hydrochloride, formsulfite or alkanolamine-sulfite adducts.
• the development can be followed by stopping, fixing and stabilizing. Development and the subsequent steps can be effected at a temperature below about 20° C., or higher temperatures, and, if desired, at above about 30° C., and preferably at about 32° to 60° C. In these cases, all of the steps need not always be effected at the same temperature.
• the light-sensitive materials for color photography of this invention are developed, after exposure, to form color images.
• Development processing basically includes at least one color development step and, optionally, a pre-hardening step, a neutralizing step, a first development (black-and-white development) step, etc.
• the above steps and the subsequent steps can be effected at a temperature below about 20° C., or higher temperatures, and, if desired, at above about 30° C., and preferably at about 32° to 60° C. Again, the steps need not always be effected at the same temperature, and they can be carried out at higher or lower temperatures.
• Color developers are alkaline aqueous solutions containing a compound whose oxidized product reacts with a color coupler to form a dye, that is, containing, as a developing agent, p-phenylenediamines such as N,N-diethyl-p-phenylenediamine, N,N-diethy-3-methyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline and N-ethyl-N- ⁇ -hydroxyethyl-p-phenylenediamine, or salts thereof such as the hydrochlorides, sulfates and sulfites thereof.
• p-phenylenediamines such as N,N-diethyl-p-phenylenediamine, N,N-diethy-3-methyl-p
• the alkaline aqueous solution has a pH higher than about 8, preferably from 9 to 12.
• the compounds as described in U.S. Pat. Nos. 2,193,015 and 2,592,364, and Japanese Patent Application (OPI) No. 64,933/73 can also been used as a developing agent.
• the color developers can contain, in addition to the above developing agent, a salt such as sodium sulfate; a pH modifier such as sodium hydroxide, sodium carbonate or sodium phosphate; a buffer, for example, an acid such as acetic acid or boric acid, or a salt thereof; and a development accelerator, for example, various pyridinium compounds, cationic compounds, potassium nitrate and sodium nitrate as described in U.S. Pat. Nos.
• the color developers can contain an antifogging agent, for example, alkali metal bromides, alkali metal iodides, nitrobenzimidazoles as described in U.S. Pat. Nos. 2,496,940 and 2,656,271, as well as mercaptobenzimidazole, 5-methylbenztriazole, 1-phenyl-5-mercaptotetrazole, compounds for rapid processing as described in U.S. Pat. Nos. 3,113,864, 3,342,596, 3,295,976, 3,615,522 and 3,597,199, thiosulfonyl compounds as described in British Pat. No. 972,211, phenazine-N-oxides as described in Japanese Patent Publication No.
• an antifogging agent for example, alkali metal bromides, alkali metal iodides, nitrobenzimidazoles as described in U.S. Pat. Nos. 2,496,940 and 2,656,271, as well as mercaptobenzimid
• the developers can contain a diffusible yellow forming coupler as described in U.S. Pat. Nos. 3,510,306 and 3,619,189 and Japanese Patent Publication Nos. 33,775/65 and 3,664/69; a diffusible magenta forming coupler as described in German Patent Application (OLS) No. 2,016,587, U.S. Pat. Nos. 2,369,489, 2,600,788, 3,152,896 and 3,615,502, and Japanese Patent Publication No. 13,111/69; and a diffusible cyan forming coupler as described in U.S. Pat. Nos. 3,002,836 and 3,542,552, and British Patent No. 1,062,190.
• OLS German Patent Application
• the light-sensitive material for color photography of this invention can also be subjected to processings prior to color development.
• a prehardening bath is used as a processing solution prior to the development step.
• An aqueous solution containing one or more aldehydes is generally used as a prehardening bath.
• Aldehydes have the effect of reacting with gelatin, that is one of the components of the photographic emulsion, thereby to harden the same.
• Suitable aldehydes include aliphatic aldehydes (formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, pyruvic aldehyde, etc.) as described in U.S. Pat. No. 3,232,761, and aromatic aldehydes as described in U.S. Pat. Nos.
• the aqueous solution can contain an inorganic salt such as sodium sulfate, a pH modifier or a buffer such as borax, boric acid, acetic acid, sodium acetate, sodium hydroxide or sulfuric acid, and a development fog inhibitor, for example, an alkali metal halide such as potassium bromide.
• an inorganic salt such as sodium sulfate
• a pH modifier or a buffer such as borax, boric acid, acetic acid, sodium acetate, sodium hydroxide or sulfuric acid
• a development fog inhibitor for example, an alkali metal halide such as potassium bromide.
• a neutralizing bath for the purpose of preventing the aldehydes used in the prehardening step from being carried over into the development bath.
• the neutralizing bath contains an agent for removing aldehydes, for example, hydroxylamine, l-ascorbic acid, etc., and also contains an inorganic salt, a pH modifier or a buffer.
• an alkaline aqueous solution containing one or more of developing agents such as hydroquinone, 1-phenyl-3-pyrazolidone or N-methyl-p-aminophenol is used.
• the alkaline aqueous solution also can contain an inorganic salt such as sodium sulfate, a pH adjusting agent or a buffer such as borax, boric acid, sodium hydroxide or sodium carbonate, and a development fog inhibitor, for example, an alkali metal halide such as potassium bromide.
• the color photographic materials are usually bleached and fixed. Bleach and fixation can be combined and, thus, a bleach-fix bath can be used.
• Many compounds can be used as a bleaching agent, but of these compounds, generally ferricyanide salts, dichromate salts, water-soluble iron (III) salts, water-soluble cobalt (III) salts, water-soluble copper (II) salts, water-soluble quinones, nitrosophenols, complex salts of an organic acid and a polyvalent cation such as iron (III), cobalt (III) or copper (II) (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid or N-hydroxyethylethylenediaminetriacetic acid, malonic acid, tartaric acid, malic acid, diglycolic acid, or dithioglycolid acid, 2,6-dipicolinic acid copper complex salt,
• any known fixing solutions can be used.
• ammonium thiosulfate, sodium thiosulfate or potassium thiosulfate can be used as a fixing agent in an amount of about 50 to 200 g/liter and, in addition, a stabilizing agent such as sulfite salts or metabisulfite salts, a hardening agent such as potassium alum, a pH buffer such as acetate salts or borate salts, and the like can be present in the fixing solution.
• the fixing solutions have a pH of about 3 to 12, generally a pH of about 3 to 8.
• Image-stabilizing baths can also be employed according to the techniques as described in U.S. Pat. Nos. 2,515,121, 2,518,686 and 3,140,177.
• An alkali-processed gelatin having an isoelectric point of a pH of 4.9 was used as a binder for each layer except the uppermost layer.
• binders for the uppermost layer acid-processed gelatin having an isoelectric point of a pH of 9.0 or alkali-processed gelatin having an isoelectric point of a pH of 4.9, benzenesulfonyl chloride-processed gelatin or phenylisocyanate-processed gelatin as a gelatin derivative, and styrene-sodium maleate copolymer or acrylonitrile-sodium acrylate copolymer as a synthetic high molecular weight material containing carboxyl groups or the salts thereof as a binder for each layer for except the uppermost layer were used in the ratio (% by weight) shown in Table 1 below.
• the processing baths employed had the following composition.
• the samples were cut into 4 cm square pieces.
• the pieces were placed, in a manner such that they did not overlap each other, in a container kept at a temperature of 30° C. and a relative humidity of 90% for 2 days.
• the uppermost layer of one light-sensitive layer and the backing layer of another light-sensitive layer were superimposed, and then the assembly was kept for 24 hours with weight of 50 g/cm 2 being placed thereon to further moisture condition.
• these samples were peeled off, and the adhered area was measured, the ratio of the adhered portions being determined as a percentage.
• Table 3 The results of reticulation and adhesion of Samples 1 to 6 are shown in Table 3 below.
• a red-sensitive silver halide emulsion layer, an intermediate layer, a green-sensitive silver halide emulsion layer and a yellow filter layer were coated in that order on an undercoated cellulose triacetate support in the same manner as in Example 1 except that 1,3,5-triacryloylperhydro-1,3,5-triazine was used as a hardening agent, and the amount thereof was 46 mg/m 2 for the red-sensitive silver halide emulsion layer, 43 mg/m 2 for the green-sensitive silver halide emulsion layer, 62 mg/m 2 for the blue-sensitive silver halide emulsion layer and 32 mg/m 2 for the intermediate layer.
• acid-processed gelatin is superior in adhesion resistance to alkali-processed gelatin, and when acid-processed gelatin is used in combination with a matting agent, an unexpected improvement is achieved in adhesion resistance.
• a silver halide emulsion layer and a protective layer were coated in that order on both sides of an undercoated polyethylene terephthalate film support and then dried at a temperature of 25° C. and a relative humidity of 60%.
• binders for the protective layer the same compositions as those in the uppermost layers in Samples 1 to 6 except acid-processed gelatin having an isoelectric point of a pH of 7.2 or alkali-processed gelatin having an isoelectric point of a pH of 5.0 were used to produce Samples 17, 18, 19, 20, 21 and 22.
• emulsion layer 50 mg of mucochloric acid as a hardening agent and 5 mg of 1-phenyl-5-mercaptotetrazole as a stabilizing agent each were used, each per g of gelatin, and silver bromoiodide containing 1.5 mol% of iodide was used.
• the emulsion layer was coated at a gelatin coverage of 2.48 g/m 2 and a silver coverage of 5.00 g/m 2 .
• a red-sensitive silver halide emulsion layer and an intermediate layer, each containing the additives shown in Table 1 hereinbefore were simultaneously coated in that order on an undercoated cellulose triacetate support using an apparatus similar to that shown in FIG. 10 of U.S. Pat. No. 2,761,791, dried at a temperature of 25° C. and a relative humidity of 60% and a 100 m length of the sample produced was wound around a core of a diameter of 10 cm.
• the same acid-processed gelatin or alkali-processed gelatin as in Example 1 was used as a binder, and the same polymethyl methacrylate as in Example 1 was used as a matting agent in an amount of 5 mg per 1 g of the binder.
• the samples wound around the core were kept at a temperature of 25° C. and a relative humidity of 60% for one week, and then unwound and examined for traces of adhesion in portions of the sample near the core.

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• 1974
  • 1974-07-01 JP JP7551674A patent/JPS5623142B2/ja not_active Expired
• 1975
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